Formation pathway of a Mn(IV), Mn(IV) bis(μ-oxo) dimer that incorporates alkali and alkaline earth cations and electron transfer properties of the dimer
Formation pathway of a Mn(IV), Mn(IV) bis(μ-oxo) dimer that incorporates alkali and alkaline earth cations and electron transfer properties of the dimer
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DOI：
10.1016/s0020-1693(99)00241-8
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发表时间：
1999-11-10
影响因子：
2.8
通讯作者：
Weintraub, ST
中科院分区：
文献类型：
--
作者：
Horwitz, CP;Ciringh, Y;Weintraub, ST
（3，3 '-17-冠-6-SALPN）Mn（II）在CH 3CN中用O-2氧化导致形成相应的Mn（IV），Mn（IV）双（μ-氧代）二聚体（2）。O-16（2）/O-18（2）标记实验，其中通过FT-IR光谱和电喷雾电离质谱（ESI-MS）分析产物，显示没有可检测量的混合同位素产物[（3，3'-17-冠-6（SALPN））Mn（IV）]（2）（mu-O-16）（mu-O-18），表明不包括Mn-O单体的简单O-O键断裂/双（μ-氧代）二聚体形成途径。将碱金属或碱土金属阳离子掺入到每个配体的冠醚部分中。加入2 equiv.将NaPF 6、KPF 6、CaTf 2或BaTf 2（Tf为[SO 3 CF 3]（-））转化为2在CH 3 CN中的浆液，形成2.2NaPF（6）、2.2KPF（6）、2.2CaTf（2）或2.2BaTf（2）。用循环伏安法对配合物进行了表征。在阳离子并入2中时，记录Mn（IV）、Mn（IV/III）（μ-O）（2）和Mn（IV/III）、Mn（III）（μ-O）（2）氧化还原过程的阳极电位偏移。一些络合物的伏安法表明，在注入第一个电子后，阳离子向Mn 2 O2核运动。All rights reserved.
The oxidation of (3,3'-17-crown-6-SALPN)Mn(II) with O-2 in CH3CN resulted in formation of the corresponding Mn(IV),Mn(IV) bis(mu-oxo) dimer (2). A O-16(2)/O-18(2) labeling experiment, in which the product was analyzed by FT-IR spectroscopy and electrospray ionization mass spectrometry (ESI-MS), showed no detectable quantity of the mixed-isotope product [(3,3'-17-crown-6(SALPN))Mn(IV)](2)(mu-O-16)(mu-O-18), suggesting a simple O-O bond cleavage/bis(mu-oxo) dimer formation pathway that does not include Mn-O monomers. Alkali or alkaline earth cations were incorporated into the crown ether portion of each ligand. Upon addition of 2 equiv. of NaPF6, KPF6, CaTf2, or BaTf2 (Tf is [SO3CF3](-)) to a slurry of 2 in CH3CN, 2.2NaPF(6), 2.2KPF(6), 2.2CaTf(2), or 2.2BaTf(2) formed. All of the complexes were characterized by cyclic voltammetry. Anodic potential shifts were recorded for the Mn(IV), Mn(IV/III)(mu-O)(2) and Mn(IV/III), Mn(III)(mu-O)(2) redox processes upon cation incorporation into 2. The voltammetry of some of the complexes was suggestive of cation motion toward the Mn2O2 core following the injection of the first electron. (C) 1999 Elsevier Science S.A. All rights reserved.